EP1205530B1

EP1205530B1 - Catalytic converting process for producing prolifically diesel oil and liquefied gas

Info

Publication number: EP1205530B1
Application number: EP00938463.7A
Authority: EP
Inventors: Jiushun Zhang; Anguo Mao; Xiaoxiang Zhong; Zhigang Zhang; Zubi Chen; Yamin Wang; Wei Wang; Shuxin Cui; Zeyu Wang; Hua Cui; Ruichi Zhang
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petrochemical Corp
Priority date: 1999-06-23
Filing date: 2000-06-20
Publication date: 2015-07-22
Anticipated expiration: 2020-06-20
Also published as: NO20016317D0; US6416656B1; NO20016317L; NO334807B1; JP2003503580A; EP1205530A1; JP4361234B2; WO2001000750A1; EP1205530A4

Description

Background of the Invention

The present invention relates to a process for catalytic cracking of hydrocarbon oils in the absence of hydrogen, and specifically relates to a process for catalytic cracking of petroleum hydrocarbon stocks in the absence of hydrogen to increase simultaneously the yields of diesel oil and liquefied gas.
Liquefied gas is one of the important petrochemical products, of which light olefins are important chemical raw materials of high commercial value. Diesel oil has high heat efficiency and the exhaust tail gas from vehicles running on diesel oil contains less harmful constituents, so it meets the more and more rigorous requirements for environmental protection all over the world. Thus, following the increase in the number of vehicles running on diesel oil, the market demand for diesel oils is also growing.
Diesel oil comes mainly from fraction oils produced by the primary and secondary processing of crude oil. In the primary processing, i.e. the atmospheric and vacuum distillation, the yield of diesel fractions from crude oil is fixed, so no potential can be tapped. In the secondary processing, catalytic cracking is usually adopted for producing diesel oil. Featuring large-volume treatment and flexible operation conditions, this process of catalytic cracking is an important means for improving the yields of liquefied gas and diesel oil.
CN1031834A discloses a catalytic cracking process for producing more light olefins. Although this process can produce large quantities of liquefied gas, but its yield of diesel oil is relatively low, generally lees than 10wt%, and moreover it requires a special catalyst and processing unit.
CN1085885A discloses a method for obtaining higher yields of liquefied gas and gasoline under the following reaction conditions: a reaction temperature of 480°-550°C, a pressure of 130-350KPa, a WHSV of 1-150h^-1, a catalyst/oil ratio of 4-15, and a steam/hydrocarbon stock weight ratio of 0.05-0.12:1. The yield of liquefied gas in the reaction products is 30-40wt%, but that of diesel oil is comparatively low.
CN1160746A discloses a catalytic cracking process for raising the octane number of low-grade gasoline fractions, wherein a low-grade gasoline is introduced into a riser reactor through its lower part and the reaction is curried out under the conditions of a reaction temperature of 600°-730°C, a WHSV of 1-180h^-1, and catalyst/oil ratio of 6-180, then a high octane gasoline is mainly obtained. The feedstocks employed in this process are low-grade gasolines, such as straight-run gasoline, coker gasoline and so on, and the yields of liquefied gas and diesel oil in the reaction products are 24-39wt% and 0.5-2.3wt% respectively.
USP3, 784, 463 discloses a process carried out in a reaction system comprising at least two riser reactors, wherein a low-grade gasoline is introduced into one of the riser reactors and catalytic cracking reaction occurs. By this process, the gasoline octane number and yield of liquefied gas are improved. However, this process cannot give higher yield of diesel oil, and it requires that the reaction unit should be revamped by adding at least another riser.
USP5,846,403 discloses a process of recracking of catalytic naphtha to obtain a maximum yield of light olefins. The process is carried out in a riser reactor comprising two reaction zones, namely an upstream reaction zone in the lower part of the reactor and a downstream reaction zone in the upper part. In the upstream reaction zone, the feedstock is a light catalytic naphtha (having a boiling point below 140°C), and the reaction conditions are: an oil-catalyst contact temperature of 620°-775°C, an oil and gas residence time of less than 1.5 sec., a catalyst/oil ratio of 75-150, and the proportion of steam accounting for 2-50wt% the weight of naphtha, while in the downstream reaction zone, the feedstock is a conventional catalytic cracking stock (having a boiling point of 220°-575°C), and the reaction conditions are: a temperature of 600°-750°C and an oil and gas residence time of less than 20 sec. Compared with conventional catalytic cracking, the yields of liquefied gas and light cycle oil (i.e. diesel oil) of this process increase by 0.97-1.21 percentage points and 0.13-0.31 percentage points higher.
CN1034949A discloses a process for converting petroleum hydrocarbons in which the stocks, ethane, gasoline, catalytic cracking stock and cycle oil, are successively upwardly introduced into a riser reactor through its lowermost part. This process is mainly aimed at producing light olefins, but the total yield of gasoline, diesel oil and liquefied gas decreases.
EP0369536A1 disclosed a process for catalytic cracking hydrocarbon feedstock, in which a hydrocarbon feedstock is charged into the lower part of the riser reactor wherein said hydrocarbon feedstock is admixed with freshly regenerated cracking catalyst, and a recycle portion of a light liquid hydrocarbon stream is charged into the riser zone at a level above the hydrocarbon feedstock charging level. This process operates in such a manner to produce maximum quantities of fuel oil, or alternatively to produce maximum quantities of olefins in different conditions, but can't increase the yields of diesel oil and of olefins simultaneously.
US P4,422,925 discloses a process for fluidized catalytic cracking hydrocarbon feedstock for producing gaseous olefins, which comprises charging gaseous C₂ to C₃ rich stock into the lowermost portion of the riser reaction zone to contact with hot freshly regenerated catalyst and charging heavy hydrocarbon stock to an upper section, of the riser, and introducing naphtha or gas oil into a section between said lower and upper sections of said riser. This process can produce high yield of light olefins but the increment of yield of diesel oil is very small.
US P3894932 disclosed a method for converting hydrocarbons which comprises passing C₃-C₄ gaseous hydrocarbon fraction through a lower portion of a riser, introducing gas oil at one or more spaced apart downstream intervals, and introducing C₂-C₄ hydrocarbon or isobutylene or gas oil through the upper portion of the riser. This method is aimed at producing aromatics and isobutane but can't increase the yields of diesel oil and liquefied gas simultaneously.
Another method of increasing the yield of liquefied gas is by adding a catalyst promoter to the catalytic cracking catalyst. For example, USP4,309,280 discloses a method of adding a HZSM-5 zeolite in an amount of 0.01-1% by weight of the catalyst directly into the catalytic cracking unit.
USP3, 758,403 discloses a catalyst comprising ZSM-5 zeolite and large-pore zeolite (e.g. the Y-type and X- type) (in a ratio of 1:10-3:1) as active components, thereby raising the yield of liquefied gas and the gasoline octane number by a big margin, while the yields of propene and butene are increased by about 10wt%. Furthermore, CN1004878B , USP4,980,053 and CN1043520A have disclosed catalysts comprising mixtures of ZSM-5 zeolite and Y-type zeolite as active components, resulting in that remarkable increases in the yield of liquefied gas are achieved. However, this kind of methods is used to mainly increase the yield of liquefied gas by means of modifying the catalysts, while the increase in the yield of diesel oil is less.
The above-mentioned patented processes can only increase the yield of liquefied gas, but cannot increase the yield of diesel simultaneously, or if any, the yield of diesel oil is insignificant. Moreover, some of the above-mentioned patented processes require special catalysts or reaction units, or the existing units should be largely refitted to meet their specific requirements.
The object of the present invention is to provide a catalytic cracking process for increasing the yields of diesel oil and liquefied gas simultaneously on the basis of the prior art.
US 5,506,365 discloses a process for the conversion of petroleum hydrocarbons in the presence of catalyst particles in a fluidized phase in an essentially upflow or downflow tubular reaction zone. The process includes at least one stage of steam cracking of at least one light hydrocarbon fraction and a stage of catalytic cracking of at least one heavy hydrocarbon fraction. The steam cracking is carried out by contacting the light hydrocarbons and a quantity of steam equal to at least 20 percent by weight in a fluidized bed of the catalyst particles, the resulting temperature ranging from 650° to 850° C. The catalytic cracking of the heavy hydrocarbons is carried out by injection of the effluents from the upstream section of the reaction zone into the catalyst suspension in such a way that the temperature of the mixture ranges from 500° to 650° C. and is then reduced to a temperature ranging 475° to 550° C.
US 5,616,237 discloses a fluid catalytic cracking unit equipped with multiple feed injection points along the length of the riser is operated such that portions of the same fresh feed are charged to different feed injection points. Preferably, the hydrocarbon fresh feed can be split into two or more non-distinct fractions, with one fraction charged to the bottom injection point along the length of the riser reactor, and the remaining fractions charged to injection points progressively higher up along the length of the riser reactor with the temperature of the upper injection feed fractions being different from that of the lowest injection point fraction prior to entry into the FCC riser reactor. Hydrocarbon products from the cracking process can be recycled to one or more of the various injection points along the length of the riser.

Summary of the Invention

A process for catalytic cracking hydrocarbon stocks to increase simultaneously the yields of diesel oil and liquefied gas, carrying out in a riser or fluidized-bed reactor, wherein said reactor comprises a gasoline cracking zone, a heavy oil cracking zone, a light oil cracking zone and an optional termination reaction zone, wherein said process comprises the following steps:

(i) Gasoline stock and an optional pre-lifting medium are charged into the gasoline cracking zone of the reactor, contact a catalytic cracking catalyst to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the heavy oil cracking zone; wherein in the gasoline cracking zone, the reaction temperature is 620-680°C, the reaction pressure is 100-230 KPa, the residence time is 0.2-1.5 sec., the weight ratio of catalyst to gasoline stock is 20-80, and the temperature of the regenerated catalyst is 660-710°C;
(ii) One of the stocks selected from the mixture of conventional catalytic cracking feed and slurry, the mixture of conventional catalytic cracking feed and heavy cycle oil, and the mixture of conventional catalytic cracking feed, slurry and heavy cycle oil, is charged into the reactor through the bottom of the heavy oil cracking zone, contact the oil-gas mixture and reacted catalyst rising from the gasoline cracking zone to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the light oil cracking zone, wherein in the heavy oil cracking zone, the weight ratio of catalyst to feedstock is 5-20, and the residence time is 0.1-2 sec;
(iii) One of the stocks selected from the mixture of conventional catalytic cracking feed and slurry, the mixture of conventional catalytic cracking feed and heavy cycle oil, and the mixture of conventional catalytic cracking feed, slurry and heavy cycle oil, is charged into the reactor through the bottom of the light oil cracking zone, contact the oil-gas mixture and reacted catalyst rising from the heavy oil cracking zone to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter an optional termination reaction zone, wherein in the light oil cracking zone, the weight ratio of catalyst to feedstock is 3-15, and the residence time is 0.1-6 sec;
(iv) A reaction terminating medium is optionally charged into the reactor through the bottom of the termination reaction zone to terminate the reaction, from where the resultant oil-gas mixture and catalyst flow forward to a disengaging section to separate; and
(v) The reaction products are separated out in the fractionation system to obtain the desired liquefied gas, gasoline and diesel oil products, and the spent catalyst passes through steam stripping and then enters a regenerator and undergoes coke-burning, and then is circulated back for reuse;

Brief Description of the Drawing

The attached drawing is a schematic diagram of a riser reactor illustrating the flow of the catalytic cracking process provided by the present invention for increasing the yields of diesel oil and liquefied gas simultaneously. The parts of the riser reactor are indicated by the reference signs in the drawing as follows:

The reference signs 1, 2, 9, 10, 11, 13, 14, 15, 16, 17, 18 and 19 are for the pipelines; 3 for the riser reactor, wherein I is for gasoline cracking zone, II for heavy oil cracking zone, III for light oil cracking zone, and IV for termination reaction zone; 4 for disengaging section; 5 for steam stripper; 6 for slant pipe (spent catalyst); 7 for regenerator; 8 for slant pipe (regenerated catalyst); and 12 for fractionation system.

Detailed Description of the Invention

The present invention relates to a process for catalytic cracking hydrocarbon stocks to increase simultaneously the yields of diesel oil and liquefied gas, carrying out in a riser or fluidized-bed reactor, according with claim 1.
The present invention relates to a process for catalytic cracking hydrocarbon stocks to give simultaneously higher yields of diesel oil and liquefied gas, carrying out in a riser or fluidized-bed reactor, wherein said reactor comprises a gasoline crackling zone, a heavy oil cracking zone, a light oil cracking zone and a optional termination reaction zone, wherein said process comprises the following steps:

(a) Gasoline stock and an optional pre-lifting medium are charged into the gasoline cracking zone of the reactor, contact a catalytic cracking catalyst to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the heavy oil cracking zone;
(b) Conventional catalytic cracking feed mixed with slurry and/or heavy cycle oil, is charged into the reactor through the bottom of the heavy oil cracking zone, contact the oil-gas mixture and reacted catalyst rising from the gasoline cracking zone to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the light oil cracking zone;
(c) Conventional catalytic cracking feed mixed with slurry and/or heavy cycle oil, is charged into the reactor through the bottom of the light oil cracking zone, contact the oil-gas mixture and reacted catalyst rising from the heavy oil cracking zone to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter an optional termination reaction zone;
(d) A reaction terminating medium is optionally charged into the reactor through the bottom of the termination reaction zone to terminate the reaction, from where the resultant oil-gas mixture and catalyst flow forward to a disengaging section to separate; and
(e) The reaction products are separated out in the fractionation system toobtain the desired liquefied gas, gasoline and diesel oil products, and the spent catalyst may pass through steam stripping and then enters a regenerator and undergoes coke-burning and then is circulated back for reuse.

Gasoline stock used in the gasoline cracking zone is a distillate oil having a boiling range of 30°-210°C selected from straight-run gasoline, catalytic gasoline and coker gasoline, or mixtures thereof, preferably a catalytic gasoline fraction having C₇"-205°C; and it can also be a narrow fraction of gasoline of a certain stage, such as that having a boiling range of 90°-140°C or 110°-210°C. Said gasoline stock may be fractions obtained from the present reaction unit per se or from other sources. Said pre-lifting medium is a dry gas or steam. The weight ratio of said pre-lifting medium to gasoline stock is in the range of 0-5:1.
In the gasoline cracking zone, the reaction temperature is about 500°-700°C, preferably about 620°-680°C; the reaction pressure is from atmospheric pressure to 300 KPa, preferably about 100-230 KPa; the residence time is about 0.1-3.0 sec, preferably about 0.2-1.5 sec; the weight ratio of catalyst to gasoline stock is about 10-150, preferably about 20-80; the weight ratio of gasoline stock to conventional catalytic cracking feed is about 0.02-0.50:1, preferably about 0.1-0.3:1; and the regenerated catalyst has a temperature of about 600°-750°C, preferably about 660°-710°C.
Said gasoline stock may be introduced from the bottom of the gasoline cracking zone or through spray nozzles arranged around the gasoline cracking zone, wherein the gasoline stock is cracked to form a liquefied gas and at the same time the sulfur and olefin contents in the gasoline are reduced while the gasoline octane number is raised. When hot catalyst comes into contact with the gasoline stock, its temperature reduces and simultaneously a trace of coke deposits on the catalyst, hence diminishing the activity of the catalyst and passivating the metals supported thereon, which is advantageous for increasing the yield of diesel oil. When the catalyst in this state contacts the conventional catalytic cracking feeds in the heavy oil cracking zone and light oil cracking zone, more diesel oil is produced. The resultant oil-gas mixture and reacted catalyst from the gasoline-cracking zone enter the heavy oil-cracking zone directly.
The conventional catalytic cracking feeds used in the heavy oil cracking zone and light oil cracking zone are selected at least one from straight-run gas oils, coker gas oils, deasphalted oils, hydrofined oils, hydrocracking tail oils, vacuum residues and atmospheric residues, or mixtures thereof. Said conventional catalytic cracking feed used in steps (b) and (C) may the same or different. A portion of about 20-95wt% of said conventional catalytic cracking feed solely, or mixed with slurry and/or heavy cycle oil, is charged into the heavy oil cracking zone; and a portion of about 5-80wt% of said conventional catalytic cracking feed solely, or mixed with slurry and/or heavy cycle oil, is charged into the light oil cracking zone.
The function of heavy oil cracking zone is to control the cracking reaction of gasoline stock, to enhance the level of heavy oil cracking severity and to ensure the conversion of heavy oil fractions so as to increase the yield of diesel oil from the feedstock in the heavy oil cracking zone and improve the feedstock's selectivity to diesel oil in the light oil cracking zone. In the heavy oil cracking zone, the weight ratio of catalyst to feedstock is about 5-20, preferably about 7-15; the oil-gas mixture residence time is about 0.1-2 sec., preferably about 0.3-1.0 sec.; and the reaction pressure is from atmospheric pressure to 300 KPa, preferably about 100-230 KPa. The portion of feedstock to be processed in the heavy oil cracking zone is relatively heavier and more difficult to be cracked.
The function of light oil cracking zone is to carry out cracking of the conventional catalytic cracking feed in this zone under an environment formed through the controlling processes of the gasoline cracking zone and heavy oil cracking zone, which is beneficial for improving the feedstocks' selectivity to diesel oil in the heavy oil cracking zone and light oil cracking zone. In the light oil cracking zone, the weight ratio of catalyst to feedstock is about 3-15, preferably about 5-10; the oil-gas mixture residence time is about 0.1-6 sec., preferably about 0.3-3 sec.; and the reaction pressure is from atmospheric pressure to 300 KPa, preferably about 100-230 KPa. The portion of feedstock to be processed in the light oil cracking zone is relatively lighter and easier to be cracked.
The recracking of heavy cycle oil and slurry is to convert unreacted fractions of them into valuable light oil products.
A termination reaction zone can be arranged after the light oil cracking zone. The function of the termination reaction zone is to diminish secondary cracking of light oils from the heavy oil cracking zone and light oil cracking zone, to increase the yield of diesel oil and to control the degree of conversion of the catalytic stocks as a whole. Said reaction terminating medium is selected at least one from waste water, softened water, recycle oils, heavy oil fractions, coker gas oils, deasphalted oils, straight-run gas oils and hydrocracking tail oils, or mixtures thereof. Depending on the type of reaction terminating medium used and the operation parameters in the heavy oil cracking zone and light oil cracking zone, particularly that of the light oil cracking zone, the weight ratio of reaction terminating medium to conventional catalytic cracking feed is about 0-30wt%. Controlled by the quantity of terminating medium injected, the temperature in the reaction termination zone is in the range of about 470°-550°C, and the material residence time is about 0.2-3.0 sec.
The catalyst applicable in the process according to the present invention can be one comprising at least one active component selected from Y-type or HY-type zeolites with or without rare earth, ultra-stable Y-type zeolites with or without rare earth, zeolites of ZSM-5 series, or high-silica zeolites having pentatomic ring structure and β -zeolites, or mixtures thereof, and can also be an amorphous silica-alumina catalyst. In short, all the catalytic cracking catalysts can be applied in the process according to the present invention.
Said riser or fluidized bed reactor comprising a gasoline cracking zone, a heavy oil cracking zone, a light oil cracking zone and a termination reaction zone has a total height of 10-50 m, wherein the heights of the zones account for 2-20%, 2-40%, 2-60% and 0-40% respectively; more accurately, the height of each of the four zones is determined in accordance with the specific operating parameters required in each reaction zone.
The process according to the present invention can be carried out in conventional catalytic cracking reactors. However, since the gasoline cracking zone in certain existing catalytic cracking units is to long, it has to be refitted, for example, the feed inlet in the gasoline cracking zone has to be rearranged at a higher location. The present process can also be carried out in reactors with a gasoline cracking zone of different structures.
The process of the present invention is further illustrated with reference to the attached drawing (exemplified with riser reactor).
The flow scheme shows the catalytic cracking process for higher yields of both diesel oil and liquefied gas, but the shape and dimensions of the riser reactor are not restricted to what is shown in the schematic diagram, whereas they are determined by the specific conditions of operation.
The flow scheme of the process according to the present invention is as follows:

A gasoline stock and a pre-lifting medium from pipelines 1 and 2 respectively are charged in a preset ratio into the riser reactor 3 through a location at a height of 0-80% of the gasoline cracking zone I contact a catalyst, which is a fresh one or a regenerated one, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the heavy oil cracking zone II; a portion of conventional catalytic cracking feed solely from pipeline 13, or mixed with a recycling slurry from pipeline 16 and/or heavy cycle oil from pipeline 17, is charged into the reactor via pipeline 13 through the bottom of the heavy oil cracking zone II contacts the reactant oil-gas mixture and catalyst rising from the gasoline cracking zone, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the light oil cracking zone III; another portion of conventional catalytic cracking feed solely from pipeline 14, or mixed with a recycling slurry from pipelines 16 and 18 and /or heavy cycle oil from pipelines 17 and 19, is charged into the reactor via pipeline 14 through the bottom of the light oil cracking zone contacts the reactant oil-gas mixture and catalyst rising from the heavy oil cracking zone, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the termination reaction zone IV; optionally, a reaction terminating medium from pipeline 15 is charged into the reactor through the bottom of the termination reaction zone IV, from which the reactant oil-gas mixture and spent catalyst flow into the disengaging section 4 with or without a dense fluidized bed reactor, and then the oil-gas mixture and steam via pipeline 11 enter the fractionation system 12 and are separated into dry gas, liquefied gas, gasoline, diesel oil, heavy cycle oil and slurry, and then the slurry can be circulated back to the heavy oil cracking zone via pipelines 16 and 13 in sequence, or to the light oil cracking zone via pipelines 16, 18 and 14 in sequence; and the heavy cycle oil can be circulated back to the heavy oil cracking zone via pipelines 17 and 13 in sequence, or to the light oil cracking zone via pipelines 17, 19 and 14 in sequence. The spent catalyst enters the steam stripper 5 for steam stripping, and then enters the regenerator 7 via the slant pipe 6 to undergo coke-burning and regeneration in the presence of air; the air is introduced into the regenerator 7 via pipeline 9, and flue gas is discharged therefrom via pipeline 10, and the hot regenerated catalyst is circulated back to the bottom of the gasoline cracking zone of the riser reactor for reuse.

The advantages of the present invention are embodied in the following points:

1. The process of the present invention can be carried out in an existing conventional catalytic cracking unit, which need not to be revamped in large scale, and it does not require special catalyst either, while the yields of liquefied gas and diesel oil can be increased by a big margin;
2. In the gasoline cracking zone, when the gasoline stock and hot catalyst comes into contact, a trace of coke deposited on the catalyst will cause passivation of the metals supported on the catalyst, hence reducing the adverse effects of the metals on product distribution. Since a large portion of strong acid sites on the zeolite and the matrix are covered by the trace of coke, this is beneficial for inhibiting coke-forming tendency during cracking of conventional catalytic cracking feed as well as for improving the selectivity to diesel oil;
3. In respect of the portion of relatively light fractions in the feedstock which can be easily cracked, the measures of operating at lower temperature with less rigorous reaction severity, shorter contact cracking and preventing secondary cracking can effectively improve the selectivity to diesel oil;
4. As sulfur contained in the gasoline stock is mainly distributed in the heavy components, the reaction in the gasoline cracking zone of the riser reactor occurs to crack selectively the heavy components therein, thus the sulfur content can be reduced remarkably,
5. In the process according to the present invention, the gasoline stock injected into the reactor can substitute completely or partially for the pre-lifting steam, as a result, the energy consumption of the reaction unit and waste water discharged therefrom are reduced, so this is beneficial for environment protection as well as for diminishing hydrothermal deactivation of the catalyst; and
6. The gasoline octane number can be maintained at a higher level or raised, while olefins of gasoline can be reduced.

Examples

The process of the present invention is further illustrated by the following non-limiting examples.
The properties of feedstocks and catalysts used in the examples are shown in Tables 1 and 2 respectively. The conventional catalytic cracking feed used was vacuum gas oil mixed with 17wt%, 18wt% of vacuum residues, and the gasoline stocks were the catalytic gasolines formed in the reaction unit. Catalysts A and B were products of the Qilu Catalysts Plant of the SINOPEC, and catalyst C was a product of the Lanzhou Catalysts Plant of the CNPC.

Comparative Example 1

This example was conducted to demonstrate that the yields of liquefied gas and diesel oil can be increased simultaneously by the process of the present invention. The process was carried out in a pilot plant riser reactor.
The total height of the reactor was 10 m, wherein the heights of the gasoline cracking zone, heavy oil cracking zone, light oil cracking zone and termination reaction zone were 1 m, 2 m, 5 m, and 2 m respectively.
The pre-lifting steam and catalytic gasoline (having a RON and MON of 92.4 and 79.1 respectively and an olefin content of 47.5wt%) in a weight ratio of 0.05:1 were charged into the reactor through a location at a height of 40% the height of the gasoline cracking zone, contacted catalyst A, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the heavy oil cracking zone; a portion of 65wt% of stock A and 100wt% of heavy cycle oil were charged into the reactor through the bottom of heavy oil cracking zone, contacted the reactant oil-gas mixture and catalyst from the gasoline cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the light oil cracking zone; a portion of 35wt% of stock A was charged into the reactor through the bottom of light oil cracking zone, contacted the reactant oil-gas mixture and catalyst from the heavy oil cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the termination reaction zone; softened water in an amount of 5% by weight of stock A was charged into the reactor through the bottom of the termination reaction zone; then, the resultant oil-gas mixture and reacted catalyst flowed to the separation system; then the reaction products were separated out, and the spent catalyst, passing through steam stripping, entered the regenerator and, after coke-burning, the regenerated catalyst was circulated back for reuse. The weight ratio of catalytic gasoline to stock A was 0.20:1.
The reaction conditions and product distribution are shown in Table 3, from which it can be seen that the yield of liquefied gas is 16.34wt%, and the yield of diesel oil is 27.81wt%. The properties of gasoline products are shown in Table 4, from which it can be seen that the gasoline products have RON and MON of 93.2 and 80.5 respectively, an olefin content of 37.8wt% and a sulfur content of 760ppm.

Comparative Example 1A

This comparative example was conducted to demonstrate the yields of liquefied gas and diesel oil obtained from a conventional catalytic feedstock in a conventional non-sectional catalytic cracking riser reactor. The process was carried out in a pilot plant riser reactor having a total height of 10 m.
The feedstock and catalyst used in this comparative example were the same respectively as those used in Example 1. The reaction conditions and product distribution are shown in Table 3, from which it can be seen that the yield of liquefied gas is only 13.23wt%, 3.11 percentage points lower than that obtained in Example 1; and the yield of diesel oil is only 25.72wt%, 1.79 percentage points lower than that obtained in Example 1. The properties of the gasoline products are shown in Table 4, from which it can be seen that the gasoline products have a RON and MON of 92.4 and 79.1 respectively, an olefin content of 47.5wt% and a sulfur content of 870ppm.

Example 2

This example was conducted to demonstrate that the yields of liquefied gas and diesel oil can be increased simultaneously by the process of the present invention. The process was carried out in the same reactor as that used in Example 1.
The pre-lifting steam and catalytic gasoline (having a RON and MON of 92.6 and 79.4 respectively and an olefin content of 46.1wt%) in a weight ratio of 0.10:1 were charged into the reactor through a location at a height of 60% the height of the gasoline cracking zone, contacted catalyst B, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the heavy oil cracking zone; a portion of 40wt% of stock A and all the slurry and heavy cycle oil were charged into the reactor through the bottom of heavy oil cracking zone, contacted the reactant oil-gas mixture and catalyst from the gasoline cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the light oil cracking zone; a portion of 60wt% of stock A and all the recycling heavy cycle oil were charged into the reactor through the bottom of light oil cracking zone, contacted the reactant oil-gas mixture and catalyst from the heavy oil cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the termination reaction zone; softened water in an amount of 10% by weight of stock A was charged into the reactor through the bottom of the termination reaction zone; then, the resultant oil-gas mixture and reacted catalyst flowed to the separation system; then the reaction products were separated out, and the spent catalyst, passing through steam stripping, entered the regenerator and, after coke-burning, the regenerated catalyst was circulated back for reuse. The weight ratio of catalytic gasoline stock to stock A was 0.08:1.
The reaction conditions and product distribution are shown in Table 5, from which it can be seen that the yield of liquefied gas is 16.68wt%, and the yield of diesel oil is 27,56wt%. The properties of gasoline products are shown in Table 6, from which it can be seen the gasoline products have RON and MON of 92.8 and 80.2 respectively, an olefin content of 43.4wt% and a sulfur content of 601ppm.

Comparative Example 2

This comparative example was conducted to demonstrate the yields of liquefied gas and diesel oil obtained from a conventional catalytic feedstock in a conventional non-sectional catalytic cracking riser reactor. The process was carried out in a pilot plant riser reactor having a total height of 10 m.
The feedstock and catalyst used in this comparative example were the same respectively as the conventional catalytic cracking feed and catalyst used in Example 2. The reaction conditions and product distribution are shown in Table 5, from which it can be seen that, in the absence of a gasoline stock, the yield of liquefied gas is only 15.23wt%, 1.36 percentage points lower than that obtained in Example 2; and the yield of diesel oil is only 25.79wt%, 1.77 percentage points lower than that obtained in Example 2. The properties of the gasoline products are shown in Table 6, from which it can be seen that the gasoline products have a RON and MON of 92.6 arid 79.4 respectively, an olefin content of 46. 1wt% and a sulfur content of 850ppm.

Example 3

This example was conducted to demonstrate that the yields of liquefied gas and diesel oil can be increased simultaneously by the process of the present invention. The process was carried out in a pilot plant riser reactor, the same as that used in Example 1.
The pre-lifting steam and catalytic gasoline (having a RON and MON of 92.6 and 79.4 respectively and an olefin content of 46.1wt%) in a weight ratio of 0.06:1 were charged into the reactor through a location at a height of 40% the height of the gasoline cracking zone, contacted the catalyst B, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the heavy oil cracking zone; a stock A of 75wt% and all the recycling slurry were charged into the reactor through the bottom of heavy oil cracking zone, contacted the oil-gas mixture and catalyst from the gasoline cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the light oil cracking zone; a stock A of 25wt% and all the recycling heavy cycle oil were charged into the reactor through the bottom of light oil cracking zone, contacted the oil-gas mixture and catalyst from the heavy oil cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the termination reaction zone; softened water in an amount of 5% by weight of stock A was charged into the reactor through the bottom of the termination reaction zone; then, the resultant oil-gas mixture and reacted catalyst flowed to the separation system; then the reaction products were separated out, and the spent catalyst, passing through steam stripping, entered the regenerator and, after coke-burning, the regenerated catalyst was circulated back for reuse. The weight ratio of catalytic gasoline stock to stock A was 0.15:1.
The reaction conditions and product distribution are shown in Table 5, from which it can be seen that the yield of liquefied gas is 18.44wt%, and the yield of diesel oil is 28.00wt%. The properties of gasoline products are shown in Table 6, from which it can be seen that the gasoline products have RON and MON of 93.6 and 80.7 respectively, an olefin content of 39.9wt% and a sulfur content of 780ppm.

Comparative Example 4

This example was conducted to demonstrate that the yields of liquefied gas and diesel oil can be increased simultaneously by the process of the present invention. The process was carried out in a pilot plant riser reactor, the same as that used in Example 1.
The pre-lifting steam and catalytic gasoline (having a RON and MON of 90.1 and 79.8 respectively and an olefin content of 51.2wt%) in a weight ratio of 0.09:1 were charged into the reactor through a location at a height of 20% the height of the gasoline cracking zone, contacted the catalyst C, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the heavy oil cracking zone; a stock B of 60wt% and a portion of 80wt% of the recycling slurry were charged into the reactor through the bottom of heavy oil cracking zone, contacted the reactant oil-gas mixture and catalyst from the gasoline cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the light oil cracking zone; a stock B of 40wt% and all the recycling heavy cycle oil were charged into the reactor through the bottom of light oil cracking zone, contacted the reactant oil-gas mixture and catalyst from the heavy oil cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the termination reaction zone; catalytic gasoline in an amount of 5% by weight of stock B was charged into the reactor through the bottom of the termination reaction zone; then, the resultant oil-gas mixture and reacted catalyst flowed to the separation system; then the reaction products were separated out, and the spent catalyst, passing through steam stripping, entered the regenerator and, after coke-burning the regenerated catalyst was circulated back for reuse. The weight ratio of catalytic gasoline stock to stock B was 0.10:1.
The reaction conditions and product distribution are shown in Table 7, from which it can be seen that the yield of liquefied gas is 20.49wt%, and the yield of diesel oil is 28.45wt%. The properties of gasoline products are shown in Table 8, from which it can be seen that the gasoline products have RON and MON of 90.5 and 80.2 respectively, an olefin content of 45.9wt% and a sulfur content of 314ppm.

Comparative Example 3

This comparative example was conducted to demonstrate the yields of liquefied gas and diesel oil obtained from a conventional catalytic feedstock in a conventional non-sectional catalytic cracking riser reactor. The process was carried out in a pilot plant riser reactor having a total height of 10 m.
The feedstock and catalyst used in this comparative example were the same respectively as the conventional catalytic cracking feed and catalyst used in Example 4. The reaction conditions and product distribution are shown in Table 7, from which it can be seen that, in the absence of a gasoline stock, the yield of liquefied gas is only 18.48wt%, 2.01 percentage points lower than that obtained in Example 4; and the yield of diesel oil is only 26.61wt%, 1.84 percentage points lower than that obtained in Example 4. The properties of gasoline products are shown in Table 8, from which it can be seen that the gasoline products have a RON and MON of 79.8 and 90.1 respectively, an olefin content of 51.2wt% and a sulfur content of 394ppm.

Comparative Example 5

This example was conducted to demonstrate that the yields of liquefied gas and diesel oil can be increased simultaneously by the process of the present invention. The process was carried out in a pilot plant riser reactor, the same as that used in Example 1.
The catalytic gasoline (having a RON and MON of 90.1.and 79.8 respectively and an olefin content of 51.2wt%) was charged into the reactor through the bottom of the gasoline cracking zone, contacted the catalyst C, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the heavy oil cracking zone; 100wt% of stock B and all the recycling slurry were charged into the reactor through the bottom of heavy oil cracking zone, contacted the reactant oil-gas mixture and catalyst from the gasoline cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the light oil cracking zone; all the recycling heavy cycle oil was charged into the reactor through the bottom of light oil cracking zone, contacted the oil-gas mixture and catalyst from the heavy oil cracking zone, and then the resultant oil-gas mixture and reacted catalyst rose up and entered the termination reaction zone; catalytic gasoline, in an amount of 10wt% the weight of stock B was charged into the reactor through the bottom of the termination reaction zone; then, the resultant oil-gas mixture and reacted catalyst flowed to the separation system; then the reaction products were separated out, and the spent catalyst, passing through steam stripping, entered the regenerator and, after coke-burning, the regenerated catalyst was circulated back for reuse. The weight ratio of catalytic gasoline stock to stock B was 0.049:1.

The reaction conditions and product distribution are shown in Table 7, from which it can be seen that the yield of liquefied gas is 18.98wt%, and the yield of diesel oil is 27.04wt%. The properties of gasoline products are shown in Table 8, from which it can be seen that the gasoline products have RON arid MON of 90.3 and 79.8 respectively; an olefin content of 48.8wt% and a sulfur content of 365ppm.

Table 1

Conventional catalytic cracking feed	A	B
Composition of Conventional catalytic cracking feed, wt%
Vacuum gas oil	82	83
Vacuum residue	18	17
Density (20°C), g/cm³	0.9053	0.8691
Viscosity, mm²/sec
80°C	23.88	7.999
100°C	13.60	5.266
Conradson residue, wt%	2.3	1.65
Pour point, °C	45	33
Group composition, wt%
Saturates	61.3	77.9
Aromatics	27.8	14.2
Resin	10.3	7.5
Asphaltenes	0.6	0.4
Elementary composition, wt%
Carbon	86.27	86.21
Hydrogen	12.60	13.36
Sulfur	1.12	0.27
Nitrogen	0.23	0.27
Metal contents, ppm
Fe	10.4
Ni	3.5	-
Cu	<0.1	-
V	3.9	-
Na	<0.1	-
Distillation range, °C
IBP	268	213
5%	370	301
10%	400	328
30%		375
50%	480	418
70%	521	466
Dry point	-

Table 2

Catalyst	A	B	C
Trade name	RHZ-300	MLC-500	LV-23

Chemical composition, wt%
Al₂O₃	42.0	44.7	51.7
Fe₂O₃	0.42	0.38

Physical properties
Specific surface area, m²/g	182	203	220
Pore volume, ml/g	1.93	2.14	2.39
Apparent density,g/cm³	0.8382	0.7921	0.7654

Screen composition, %
0-40 µm	7.4	8.5	22.4
0-80 µm	66.4	66.3	-
0-110 µm	90.0	87.2	81.9
0-150 µm	98.9	95.9	-

Table 3

	Comp. Example 1	Comp. Ex. 1A
Pre-lifting steam/gasoline stock weight ratio	0.05	-
Pre-lifting stock/conventional catalytic cracking feed weight ratio	0.20	0
Catalyst	A	A
Reaction conditions
Temperature, °C		500
Gasoline cracking zone	640	-
Heavy oil cracking zone	580	-
Light oil cracking zone	507	-
Residence time, sec.		1.9
Gasoline cracking zone	1	-
Heavy oil cracking zone	0.4	-
Light oil cracking zone	1	-
Catalyst/oil ratio		5
Gasoline cracking zone	25	-
Heavy oil cracking zone	6.7	-
Light oil cracking zone	5	-
Pressure (gauge), KPa	90	90
Regenerated catalyst temp., °C	680	660
Product distribution, wt%
Dry gas	3.56	3.08
Liquefied gas	16.34	13.23
Gasoline	37.96	43.61
Diesel oil	26.51	24.72
Slurry	9.25	9.23
Coke	6.38	6.13
Total	100.00	100.00

Table 4

	Comp. Example 1	Com. Examp. 1A
Density (20°C), kg/m³		0.7503
Octane number
RON	93.2	92.4
MON	80.5	79.1
Olefin content, wt%	37.8
Induction period, min.	632	545
Existent gum, mg/100ml	2	3
Sulfur, ppm	760	870
Nitrogen, ppm	21	27
Carbon, wt%	87.20	86.65
Hydrogen, wt%	12.75	13.26
Distillation range, °C
IBP	45	41
10%	76	71
30%	106
50%	127	123
70%	148	148
90%	169	171
EBP	192	195

Table 5

	Example 2	Comp. Ex 2	Example 3
Steam/gasoline stock weight ratio	0.10	-	0.06
gasoline stock/conventionalcatalytic cracking feed weight ratio	0.08	0	0.15
Catalyst	B	B	B
Reaction conditions
Temperature, °C		500
Gasoline cracking zone	660	-	645
Heavy oil cracking zone	610	-	590
Light oil cracking zone	500	-	500
Residence time, sec.		1.83
Gasoline cracking zone	0.3	-	1.1
Heavy oil cracking zone	0.4	-	0.3
Light oil cracking zone	1.89	-	1.93
Catalyst/oil ratio		6.2
Gasoline cracking zone	77	-	41.3
Heavy oil cracking zone	10.3	-	8.3
Light oil cracking zone	6.2	-	6.2
Pressure (gauge), KPa	150	150	150
Regenerated catalyst temp.,	°C 675	670	678
Product distribution, wt%
Dry gas	3.13	2.90	3.83
Liquefied gas	16.68	15.32	18.44
Gasoline	42.73	46.61	40.03
Diesel oil	27.56	25.79	28.26
Coke	9.05	8.57	8.78
Loss	0.85	0.81	0.66
Total	100.00	100.00	100.00

Table 6

	Example 2	Com. Ex. 2	Example 3
Density (20°C), kg/m³	0.7601	0.7548	0.7694
Octane number
RON	92.8	92.6	93.6
MON	80.2	79.4	80.7
Olefin content, wt%	43.4	46.1	39.9
Induction period, min.	601	556	657
Existent gum, mg/100ml	2	3	2
Sulfur, ppm	790	850	780
Nitrogen, ppm	22	26	20
Carbon, wt%	86.91	86.63	87.18
Hydrogen, wt%	13.01	13.24	12.73
Distillation range, °C
IBP	43	40	45
10%	75	70	77
30%	102	99	105
50%	124	124	127
70%	146	148	147
90%	170	172	169
EBP	192	194	192

Table 7

	Comp. Example 4	Comp. Ex 3	Comp Example 5
Steam/gasoline stock weight ratio	0.09	-	0
gasoline stock/conventionalcatalytic cracking feed weight ratio	0.10	0	0.049
Catalyst	C	C	C
Reaction conditions
Temperature, °C		500
Gasoline cracking zone	668	-	690
Heavy oil cracking zone	596	-	520
Light oil cracking zone	502	-	500
Residence time, sec.		2.60
Gasoline cracking zone	1.59	-	2.16
Heavy oil cracking zone	1.50	-	1.40
Light oil cracking zone	2.40	-	1.60
Catalyst/oil ratio		5
Gasoline cracking zone	50	-	100
Heavy oil cracking zone	8.33		5
Light oil cracking zone	5	-	5
Pressure (gauge), KPa	200	200	200
Regenerated catalyst temp.,°C	699	671	700
Product distribution, wt%
Dry gas	2.78	2.25	3.01
Liquefied gas	20.49	18.48	18.98
Gasoline	40.64	45.97	44.17
Diesel oil	28.45	26.61	27.04
Slurry	1.20	0	0
Coke	6.01	6.22	6.35
Loss	0.43	0.56	0.45
Total	100.00	100.00	100.00

Table 8

	Comp Example 4	Comp.Ex.3	Comp. Example 5
Density (20°C), kg/m³	0.7559	0.7454	0.7458
Octane number
RON	90.5	90.1	90.3
MON	80.2	79.8	79.8
Olefin content, wt%	45.9	51.2	48.8
Induction period, min.	574	515	545
Existent gum, mg/100ml	3	4	3
Sulfur, ppm	314	394	365
Nitrogen, ppm	13	17	15
Carbon, wt%	86.94	86.14	86.81
Hydrogen, wt%	13.01	13.21	13.17
Distillation range, °C
IBP	40	40	43
10%	63	62	62
30%	84	83	82
50%	110	107	108
70%	136	134	135
90%	190	190	191
EBP	197	196	195

Claims

A process for catalytic cracking hydrocarbon stocks to increase simultaneously the yields of diesel oil and liquefied gas, carrying out in a riser or fluidized-bed reactor, wherein said reactor comprises a gasoline cracking zone, a heavy oil cracking zone, a light oil cracking zone and an optional termination reaction zone, wherein said process comprises the following steps:
(i) Gasoline stock and an optional pre-lifting medium are charged into the gasoline cracking zone of the reactor, contact a catalytic cracking catalyst to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the heavy oil cracking zone; wherein in the gasoline cracking zone, the reaction temperature is 620-680°C, the reaction pressure is 100-230 KPa, the residence time is 0.2-1.5 sec., the weight ratio of catalyst to gasoline stock is 20-80, and the temperature of the regenerated catalyst is 660-710°C;

(ii) One of the stocks selected from the mixture of conventional catalytic cracking feed and slurry, the mixture of conventional catalytic cracking feed and heavy cycle oil, and the mixture of conventional catalytic cracking feed, slurry and heavy cycle oil, is charged into the reactor through the bottom of the heavy oil cracking zone, contact the oil-gas mixture and reacted catalyst rising from the gasoline cracking zone to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter the light oil cracking zone, wherein in the heavy oil cracking zone, the weight ratio of catalyst to feedstock is 5-20, and the residence time is 0.1-2 sec;

(iii) One of the stocks selected from the mixture of conventional catalytic cracking feed and slurry, the mixture of conventional catalytic cracking feed and heavy cycle oil, and the mixture of conventional catalytic cracking feed, slurry and heavy cycle oil, is charged into the reactor through the bottom of the light oil cracking zone, contact the oil-gas mixture and reacted catalyst rising from the heavy oil cracking zone to produce an oil-gas mixture, and then the resultant oil-gas mixture and reacted catalyst rise up and enter an optional termination reaction zone, wherein in the light oil cracking zone, the weight ratio of catalyst to feedstock is 3-15, and the residence time is 0.1-6 sec;

(iv) A reaction terminating medium is optionally charged into the reactor through the bottom of the termination reaction zone to terminate the reaction, from where the resultant oil-gas mixture and catalyst flow forward to a disengaging section to separate; and

(v) The reaction products are separated out in the fractionation system to obtain the desired liquefied gas, gasoline and diesel oil products, and the spent catalyst passes through steam stripping and then enters a regenerator and undergoes coke-burning and then is circulated back for reuse;
wherein the gasoline stocks are distillate oils having a boiling range of 30°-210°C selected from catalytic gasoline and coker gasoline, or mixtures thereof,
and wherein the conventional catalytic cracking feed is selected from straight-run gas oil, coker gas oil, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residue and atmospheric residue, or mixtures thereof.
A process according to claim 1, wherein said pre-lifting medium is dry gas or steam, the weight ratio of the prelifting medium to the gasoline stock is 0-0.1:1.
A process according to claim 1, wherein said gasoline stock in the gasoline cracking zone is a catalytic gasoline fraction of C7-205°C.
A process according to claim 1, wherein
in the heavy oil cracking zone, the weight ratio of catalyst to feedstock is 7-15, and the residence time is 0.3-1 sec, and
in the light oil cracking zone, the weight ratio of catalyst to feedstock is 5-10, and the residence time is 0.2-3 sec.
A process according to claim 1, wherein said conventional catalytic cracking feed used in steps (ii) and (iii) may be the same or different, the weight ratio of said feed used in step (ii) to said feed used in step (iii) is 20-95:80-5.
A process according to claim 1, wherein the weight ratio of gasoline stock to conventional catalytic cracking feed is 0.02-0.50:1.
A process according to claim 1, wherein said reaction terminating medium is selected from waste water, softened water, catalytic gasoline, coker gasoline, straight-run gasoline, cycle oil stock, heavy oil fraction, coker gas oil, deasphalted oil, straight-run gas oil and hydrocracking tail oil, or mixtures thereof, and said reaction terminating medium accounts for 0-30wt% of the conventional catalytic cracking feed.
A process according to claim 1, wherein the total height of said reactor is 10-50m, of which the heights of gasoline cracking zone, heavy oil cracking zone, light oil cracking and termination reaction zone are 2-20%, 2-40%, 2-60% and 0-40% respectively.